Detection of iron atoms by emission spectroscopy and laser-induced fluorescence in solid propellant flames.

Planar laser-induced fluorescence on atomic iron is investigated in this paper, and a measurement strategy is proposed to monitor the fluorescence of iron atoms with good sensitivity. A model is proposed to fit the experimental fluorescence spectra, and good agreement is found between simulated and experimental spectra. Emission and laser-induced fluorescence measurements are performed in the flames of ammonium perchlorate composite propellants containing iron-based catalysts. A fluorescence signal from iron atoms after excitation at 248 nm is observed for the first time in propellant flames. Images of the spatial distribution of iron atoms are recorded in the flame in which turbulent structures are generated. Iron fluorescence is detected up to 1.0 MPa, which opens the way to application in propellant combustion.

Rovibrational hybrid fs/ps CARS using a volume Bragg grating for N2 thermometry.

Coherent anti-Stokes Raman scattering (CARS) spectra of N2 in the hybrid femtosecond/picosecond regime have been recorded with 0.7 cm(-1) resolution. The Q-branch rovibrational structure has been resolved, making it suitable for gas-phase simultaneous rotational and vibrational thermometry applications. Resolving this spectral structure requires synchronization of a narrowband picosecond probe pulse with a broadband femtosecond pair of pump and Stokes pulses. It is achieved using a single femtosecond ytterbium-laser source and a volume Bragg grating in a compact experimental arrangement.

Laser-based diagnostics applied to the study of BN nanotubes synthesis.

The boron nitride nanotubes (BNNTs) synthesis, using CO2-laser vaporization of a BN target under nitrogen gas, is investigated by UV-laser induced fluorescence (LIF) of the vapor phase and UV-Rayleigh scattering (RS) of the gas-suspended nanoparticles. The LIF signal from B atoms is mainly detected in the 1.5 mm-thick region above the BN target. It originates from a boron-rich vapor region confined near the hot boron droplet formed at the target surface. Then, recombination between hot boron and N2 gas occurs through a fast condensation process as revealed by both the depletion of B atoms from the vapor phase and the RS signal arising from the grown BN nanoparticles. Fluorescence spectra exhibit a strong peak at 250 nm due to boron fluorescence and mainly to nanoparticles Rayleigh scattering. A narrow peak is observed at 210 nm and a broader peak at 189 nm. These bands are tentatively assigned to fluorescence or photoluminescence (PL) from gaseous or solid BN species respectively since both gas and solid phases coexist in the plume due to the rapid cooling process. Two very weak bands occur at 308 nm and 350 nm. They are related to PL of defects bands from BN nanostructures on the basis of ex situ PL spectra of h-BN crystallites and multi-wall BNNTs. Detection of oxygen impurities is shown feasible through LIF from BO radical which is detected just above the BN target evaporated under vacuum pressure (approximately 1 mbar). An optical diagnostic strategy is demonstrated from these first in situ observations during BNNTs synthesis.

Spatial evolutions of Co and Ni atoms during single-walled carbon nanotubes formation: measurements and modeling.

Spatial investigations of nickel and cobalt atoms and of C2 and C3 radicals are performed by laser induced fluorescence (LIF) in a continuous CO2 laser-vaporization reactor during the synthesis of single-walled carbon nanotubes. The chemical composition of the gas vaporized from bimetallic Ni/Co catalysts-carbon targets is determined using a chemical kinetic model. In this model, the evolution of Ni and Co atoms is driven by kinetics of condensation/evaporation process of pure metal clusters. Metal-carbon clusters are assumed to form from soot particles (C80) and 128-atom metal clusters. Spatial profiles of Ni and Co atoms obtained by LIF are compared with the calculations to validate the modeling and to adjust the input data. The value of the initial molar fraction of carbon-metal mixture diluted in helium is determined through a parametric study. Good agreement is found between the measured and the calculated evolution of Ni for a molar fraction of the helium diluent ranging from 10 to 15%. To fit the spatial profile of Co, the activation energy is adjusted in the evaporation rate, changing the cobalt dimer bond energy. The latter is found to be largely uncertain; and three values are tested: 167, 208, and 230 kJ x mol(-1). From comparison, the activation energy is found to be 208 kJ x mol(-1). However, the C2 LIF profiles show that the depletion of C2 is accelerated when cobalt is present. The observed Co evolutions suggest that small Co-C clusters are easier and/or faster to form compared to Ni-C clusters.

Optical transitions in single-wall boron nitride nanotubes.

Optical transitions in single-wall boron nitride nanotubes are investigated by means of optical absorption spectroscopy. Three absorption lines are observed. Two of them (at 4.45 and 5.5 eV) result from the quantification involved by the rolling up of the hexagonal boron nitride (h-BN) sheet. The nature of these lines is discussed, and two interpretations are proposed. A comparison with single-wall carbon nanotubes leads one to interpret these lines as transitions between pairs of van Hove singularities in the one-dimensional density of states of boron nitride single-wall nanotubes. But the confinement energy due to the rolling up of the h-BN sheet cannot explain a gap width of the boron nitride nanotubes below the h-BN gap. The low energy line is then attributed to the existence of a Frenkel exciton with a binding energy in the 1 eV range.

In-situ optical analysis of the gas phase during the formation of carbon nanotubes.

A reactor has been developed at ONERA to investigate the gas phase during carbon nanotube formation by laser-induced fluorescence (LIF), Laser-induced incandescence (LII), coherent anti-Stokes Raman Scattering (CARS), and emission spectroscopy. Continuous vaporization is achieved with a continuous wave CO2 laser. Optimized conditions are used for single-walled nanotube growth, that is, a graphite target doped with 2 atom % Ni and 2 atom % Co, helium as buffer gas at a flow rate of 50 ml/s, and a pressure of 300 hPa. Temperature profiles are measured by CARS on H2, and soot images are obtained by LII in the hot carbonaceous flow. LIF and spontaneous emission of the C2 radical and Ni and Co atoms are presented. Spectral investigations are conducted at 3100 and 3200 K to have an optimized pair of excitation/detection wavelengths. Spatial investigations of the relative concentrations in the hot carbonaceous flow are performed up to 3500 K. The concentrations are measured as a function of target temperature. Two regimes of vaporization are observed. Vaporization is slow up to 3350 K and becomes much faster above this temperature. The fast regime in the 3350-3500 K range corresponds to the observed spatial extent of the metal vapors region. At 3500 K, the C2 profiles obtained with and without catalysts are very different as a result of carbon coalescence as well as carbon dissolution into the metal nanoparticles when these are present in the gas phase. The shape of the C2 profile can be related to nanotube formation and growth at a target temperature of 3500 K.

Laser-induced fluorescence study of OH in flat flames of 1-10 bar compared with resonance CARS experiments.

Laser-induced fluorescence (LIF) measurements of OH were performed in flat stoichiometric CH(4)/air flames burning at 1, 3, 5, 7, and 9.6 bar, which had previously been investigated using OH resonance CARS. In the LIF study, line shape information and temperatures were extracted from excitation spectra; in addition, OH profiles as a function of height above the burner surface and an estimate of the OH concentration for the different flames were obtained. The perspectives and feasibility of quantitative fluorescence measurements in high pressure flames are discussed, particularly in comparison with the application of resonance CARS.